Lignin is currently one of the most promising biologically derived resources, due to its abundance and application in biofuels, materials and conversion to value aromatic chemicals. The need to better characterize and understand this complex biopolymer has led to the development of many different analytical approaches, several of which involve mass spectrometry and subsequent data analysis. This review surveys the most important analytical methods for lignin involving mass spectrometry, first looking at methods involving gas chromatography, liquid chromatography and then continuing with more contemporary methods such as matrix assisted laser desorption ionization and time-of-flight-secondary ion mass spectrometry. Following that will be techniques that directly ionize lignin mixtures—without chromatographic separation—using softer atmospheric ionization techniques that leave the lignin oligomers intact. Finally, ultra-high resolution mass analyzers such as FT-ICR have enabled lignin analysis without major sample preparation and chromatography steps. Concurrent with an increase in the resolution of mass spectrometers, there have been a wealth of complementary data analyses and visualization methods that have allowed researchers to probe deeper into the “lignome” than ever before. These approaches extract trends such as compound series and even important analytical information about lignin substructures without performing lignin degradation either chemically or during MS analysis. These innovative methods are paving the way for a more comprehensive understanding of this important biopolymer, as we seek more sustainable solutions for our human species’ energy and materials needs.

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基于质谱的木质素高级表征和结构分析方法：综述

木质素是目前最有前途的生物衍生资源之一，因为它在生物燃料、材料和转化为有价值的芳香化学品方面的丰富和应用。更好地表征和理解这种复杂的生物聚合物的需要导致了许多不同的分析方法的发展，其中一些涉及质谱和随后的数据分析。本综述调查了涉及质谱的木质素最重要的分析方法，首先研究了涉及气相色谱、液相色谱的方法，然后继续使用更现代的方法，如基质辅助激光解吸电离和飞行时间二次离子质谱。接下来是直接电离木质素混合物的技术——无需色谱分离——使用更温和的大气电离技术，使木质素低聚物保持完整。最后，FT-ICR 等超高分辨率质量分析仪无需主要的样品制备和色谱步骤即可实现木质素分析。随着质谱仪分辨率的提高，出现了大量互补的数据分析和可视化方法，使研究人员能够比以往更深入地探索“木质素”。这些方法提取化合物系列等趋势，甚至提取有关木质素子结构的重要分析信息，而无需在化学或 MS 分析过程中进行木质素降解。